Process for breaking petroleum emulsions



Patented Feb. 20 1951 PROCESS FOR BRE KIN Grammar EMULSIONS I Melvin De Groote, St; Louis, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd; Wilmington, Del., a corporation of Delaware No Drawing. Application December 10,1948,

Serial No. 64,460 i t This invention relates to processes or procedures particularly adapted'for preventing, breaking, or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions. This invention is a continuation-in-part of our co-= fucts, ;and the-like, in .yarious other 33111175" and, 111-,

idustries;alongi-with the method 'fori manufact'uring saidnewic'hemicallproducts o ompounds which' are' of outstanding value in 'dmulsificatioh. See our copending'appli' non, SriaI'ZNOIi G lMGI,

f ledi'December 10,19 18? I Our in\ n'antion provides an e rapidc rocessi nresqlr em tr etcl, gandswhich comprise"fine droplets ofqgnatiu'rally-occurring waterssor" bribes; dispersed in a more or less permanent state throug-houtahe oil a which constitutesgthe continuous phaseflof the 5' I J r It also, provides an economical-an rapid prob-""1 ess' for separating emulsions "which have 'been prepared under",controlledr conditions"from mineral OiL'SllChas crudeoiltand'relativelyisoft waters subsequent dcmiusifieanorr -und "tliebonditioris fiust'm entioried are 'of s'ig'ni-ficant'valu iiiremoving impurities, particularlyinof'gahi salts f ri l a t W1; f a mm etjm ascncn l applicationincludes' the rav in t e. d m ls fl jr W1 pcnent, which would e1 1 s 1:61amieht subsequn l lb come either 'phas'ebfjith ,einul'sioii,inLthefabsefice r 19 Claims. (01. 252-342) in which R is a hydrocarbon-radical having at least-q andnotmore than 12-;carbonatoms and substituted inthe 2,4,6 position; said oxyalkylated resin being characterized by the introduction into of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component.

.Briefiy stated, the present process is concerned with the breaking or resolving of petroleum emulsions by means of certain esters which are, in turn, derivatives of specific synthetic products. These products are, in turn, the oxyalkylated derivatives of certain resins hereinafter specified.

Thus, the present process is concerned with breaking petroleum emulsions of the water-inoil type characterized by subjecting the emulsion to the action of a hydrophile ester in which the acyl radical isthat of the fatty acidof drasticallyoxidized castoroil; and the alcoholic radical is that of certainl ydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyalkylationproducts of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide,

'glycidandmethylglycide, and (B) an qxyalkylation-lsuscep'tible, fusible, organic solvent soluble, ater-insoluble phenolaldehyde resin; said resin bei-ngderive'd by reaction between adifunctional -'monohydric phenol and arr-aldehyde having. not oyeiflflfcarbon atoms and reactive toward said 7 phenol? saidresin being formedin the substantial .absencefof i-trifunctional phenols; said ph enol iha h i m aw the resin molecule of a plurality of divalent radicals having theflformula (310) Min whichflRris a-membeif selectecl from the class consisting of ethylene radicals, propylene radicals, butylene radicals, .hydroxy-propylene radicals, and 2 hyldroxybutylen radicals, and nLisa numeral .varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of said ester, as well as said oxyalkylated resin, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

For purpose of convenience what is said hereinafter will be divided into four. parts. Part 1 will be concerned with the production of the resin from a difunctional phenol and an aldehyde; Part 2 will be concerned with the oxyalkylation of the resin so as to convert it into av ydrophile hydroxylated derivative; Part 3 will be concerned with the conversion of the immediately aforementioned derivative into a total or partial ester by reaction with an acid, an ester, or other functional derivative, so as to obtain a compound of the kind prev ously specified and subsequently described in detail; and Part 1 Willbe concerned with the use of such esters as demulsifiers as here'- inafter described.

PART 1 .As to the preparation of the phenol-aldehyde resins reference is made to our co-pending applications, Serial Nos. 8,730 and 8,731, both filed February 16, 1948 (both now abandoned). In such co-pending applications we described a fusible, organic solvent-soluble, water-insoluble resin polymer of the formula Insuch idealized representation n" is a numeral varying from 1 to 13 or even more, provided that theresin is fusible and organic solvent-soluble.

It is a hydrocarbon radical having at least 4-. and

not over 8 carbon atoms. In the instant application R may have as many as 12 carbon atoms, as in the case of a resin obtained from a dodecylphenol. In the instant invention it may be first suitable to describe the alkylene oxides employed as reactants, then the aldehydes, and finally the phenols, for the reason that the latter require a more elaborate description.

The alkylene oxides which may be used are the alpha-beta oxides having not more than 4 carbon atoms, to wit, ethylene oxide, alpha-beta propylene oxide, alpha-beta butylene oxide, glycide, and methyl glycide.

Any aldehyde capable of forming a methylol or a substituted methylol group and having not more than 8 carbon, atoms is satisfactory, solong as it does not possess some other functional group or structure which will conflict with the resinification reaction or with the subsequent oxyalkylation of the resin, but the use of formaldehyde, in its cheapest form of an aqueous solution, for the production of the resins is particularly advantageous. Solid polymers of formaldehyde are more expensive and higher aldehydes are both less reactive, and are more expensive.

Furthermore, the higher aldehydes may undergo other reactions which are not desirable, thus introducing difficulties into the resinification step. Thus acetaldehyde, for example, may undergo an aldol condensation, and it and most of the higher aldehydes enter into self-resinification when treated with strong acids or alkalies. On the other hand, higher aldehydes frequently beneficially affect the solubility and fusibility of a resin. Thisisillustrated, for example, by the different characteristics of the resin prepared from paratertiary amylphenol and formaldehyde on one hand, and a comparable product prepared from the same phenolic reactant and heptaldehyde 0n the other hand. The former, as shown in certain subsequent examples, is a hard, brittle, solid, whereas the latter is soft and tacky, and obviously easier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. The employment of furfural requires careful control for the reason that in addition to its aldehydic function, furfural can form vinyl condensations by virtue of its unsaturated structure. The production of resins from furfural for use in preparing reactants for the present process is most conveniently conducted Withweakalkaline catalysts .and often with alkali metal carbonates. Useful aldehydes, in addition to formaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde, Z-ethylhexanal, ethylbutyraldehyde, heptaldehyde, and benzaldehyde, furfural and glyoxal. It would appear that the use of glyoxal should be avoided due to the fact that it is tetrafunctional. However, our experience has been that, in resin manufacture and particularly as describedherein, apparently only one of the aldehydic functions enters into the resinification reaction. The inability of the other aldehydic function to enter into the reaction is presumably due to steric hindrance. Needless to say, one can use a mixture of two or more aldehydes although usually this has no advantage.

Resins of the kind which are used as intermediates in thisinvention are obtained with the use of acid catalysts or alkaline catalysts, or without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amines, and quaternary ammonium bases. It is generally accepted that when ammonia and amines are employed as catalysts they enter into the condensation reaction and, in fact, may operate by initial combination with the aldehydic reactant. The compound hexamethylenetetramine illustrates sucli a combination. In light of these various reactions it becomes difficu'lt to present any formula which would depict the structure of the various resins prior to oxyalkylation. More will be said subsequently as to the difference between the use of any alkaline catalyst and an acid cata- ..lyst; even in, the use of an alkaline catlyst there actually polycyclic although the phenolic hy- 'droxyl is not attached to a fused polycyclic nucleus. Stated another way, phenols in which the hydroxyl group is directly attached'to a condensed or fused polycyclic structure, are excluded. This matter, however, is clarified by the following consideration. The phenols herein contemplated for reaction may be indicated by the following formula:

in which R is selected from the class consisting of hydrogen atoms and hydrocarbon radicals having at least 4 carbon atoms and not more than 12 carbon atoms, with the proviso that one occurrence of R is the hydrocarbon substituent and the other two occurrences are hydrogen atoms, and with the further provision that, one or both ,of.=the, 3 fin-d v5. positions may thy! sub ."The above formula possibly cannbe rcstated more conveniently .in thetfollowing manner,- to wit, that thegphenol employed is g f the following iormula with the proviso that R ,isa hydrocarbon substituent located in the; 2,4,6 ,position', again with the, provision as, tor-,3 -or 3 ,5 methyl substir .tution. This is-v conventional nomenclature, ,num- .eberin ,thervarious', positions, in thee-usual, clock,- iwiseimanner, beginning. with the. hydroxyl Ipositionas onez. i 1 -,,i

manufacture thermoplastic phenola alde de res ins, gparticularlyfmm; formaldehyde anqla,d funetion l.phs o i, e. aphenohimwhich aonegof the three,. reactiv,e ositionser(2,4 ,6 has pyand been,substitntedsby a hydro arbon emu particularly g-bys. one; having ateleast A carb'on atoms and'not more than lzcarb onatoms, iswell known: As: has, beern previously; pointed out, ;there;is-no.aobiection.toamethyl radica pr idcd titgis presentin the 3 or,-5,positi on.a ;y

.J.AThermoplasticz, or afusibletl; bend-aldehyde resins arausually manufacturedtfor the :varnish e tradeaand oilisolubilitys ,fprimeggimportance.

Fenthis reasonithe commong reactantslemployed ther difficulty, while when a water-soluble phenol is employed some modification is usually adopted to increase the interfacial surface and thus cause reaction to take place. A common solvent is sometimes employed. Another procedure employs rather severe agitation to create a large 'int erfacial area. Once the reaction starts to a 'moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted mass and assist in hastening the reaction. We have found it desirable to employ a small proportion: of anorganic sulfor-acid as a catalyst, either alone or along with a mineral acid like sulfuric or hydrochloric acid. For example, alkylated aromatic sulfonic acids are effectively employed. Since commercial forms of such acids are commonly their alkali salts, it is sometimes convenient to use a small quantity of such alkali salt plus a small quantity of strong mineral acid, as shown in the examples below. If desired, such organic sulfo-acids may be, prepared in situ in the phenol employed, by reacting concentrated sulfuric acid with a small proportion of the phenol, In such cases Where xylene is used as a solvent and concentrated sulfuric acid is employed; some sulfonation of the xylene probably occurs to produce the sulfo-acid. Addition of a solvent such as xylene is advantageous as hereinafter described in detail. Another variation of procedure is to employ such organic sulfoacids, in the form ofytheiresalts, in connection with anaalkali-catalyzed resinificati onprocedure. -Detailed examples are; included subsequently.=, v,

sta -Another advantage in theimanufacturewofethe 5 themnoplastic orfusibletype oferesin. bystheacid :.cata;lytic':i proce.dure isw-that, since adifunctional phenol is; employed, .an GXCESSgOf an aldehyde, fon instancez formaldehyde,- maysbe employed withoutrtoo markedxa change in conditions of c 50 vrea'ctionsand ultimate; product There ills 115118115 little, if any, advantage, :howeven -in: using can ;cxcess,= rover rand above the: stoichiometric ipro- :portionsior the :reason that-asuchiexcess may be dostia-nd wasted;1-:.:For :all: practical, purposes the -.55 molar *ratio ofxformaldehyde;to phenol may: be

of one-to-one or thereaboutss a W'ith the use I of :-.-alkaline. catalyst sithasibeenzrecognized that con- ..'-70 :siderablyincreased amounts of formaldehyde may :ialdehyde;remainsiuncombinedzo s-subseque'ntly liberatedduring ,riesinificationira Structures which have been advanced to explain suchincreased use of aldehydes are the following:

OH on -o-mo-O-omo+om-O- on on H CHz-O-CH H Such structures may lead to the production of cyclic polymers instead of linear polymers. For this reason, it has been previously pointed out that, although linear polymers have by far the most important significance, the present invention does not exclude resins of such cyclic structures. v

Sometimes conventional resinification procedure is employed using either acid or alkaline catalysts to produce such low-stage resins. Such resins may be employed as such, or may be altered or converted into high-stage resins, or in any event, into resins of higher molecular weight, by heating along with the employment of vaccum so as to split as water or formaldehyde, or both. Generally speaking, temperatures employed, particularly with vacuum, may be in the neighborhood of 175 to 250 C., or thereabouts.

It may be well to point out, however, that the amount of formaldehyde used may and does usually affect the length of the resin chain. Increasing the amount of the aldehyde, such as formaldehyde, usually increases the size or molecular weight of the polymer.

In the hereto appended claims there is specified, among other things, the resin polymer containing at least 3 phenolic nuclei. Such minimum molecular size is most conveniently determined as a rule by cryoscopic method using benzene, or some other suitable solvent, for instance, one of those mentioned elsewhere herein as a solvent for such resins. As a matter of fact, using the procedures herein described or any conventional resinification procedure will yield products usually having definitely in excess of 3 nuclei. In other words, a resin having an average of 4, or 5 /2 nuclei per unit is apt to be formed as a minimum in resinification, except under certain special conditions where dimerization may occur.

However, if resins are prepared at substantially higher temperatures, substituting cymene, tetralin, etc., or some other suitable solvent which boils or reiluxes at a higher temperature, instead of xylene, in subsequent examples, and if one doubles or triples the amount of catalyst, doubles or triples the time of refluxing, uses a marked excess of formaldehyde or other aldehyde, then the average size of the resin is apt to be distinctly over the above values, for example, it may average '7 to units. Sometimes the expression low-stage resin or low-stage intermediate is employed to mean a stage having 6 or 7 units or even less'. In the appended claims we have used low-stage to mean 3 to 7 units based on average molecular weight.

The molecular weight determinations, of course; require that the product be completely soluble. in the particular solvent selected as. for instance, benzene. The molecular weight determination of such solution may involve either the freezing point as in the cryoscopic method, or, less ponveniently perhaps, .the boiling point in an'Tebullioscopic method. The advantage of the ebullioscopic method is that, in comparison with the cryoscopic method, it is more apt to insure complete solubility. One such common method to employ is'tha-t of Menzies and Wright (see J. Am. Chem. Soc. 43, 2309 and 2314 (1921)). Any suitable method for determining molecular weights will serve, although almost any procedure adopted has inherent limitations. A good method for determining the molecular weights of resins, especially solvent-soluble resins, is the cryoscopic procedure of Krumbhaar which employsdiphenylamine as a solvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co. 1947). g

Subsequent examples will illustrate the use of an acid catalyst, an alkaline catalyst, and no catalyst. As far as resin manufacture per se is concerned, we prefer to use an acid catalyst, and particularly a mixture of an organic sulfo-acid and a mineral acid, along with a suitable solvent, such as xylene, as hereinafter illustrated in detail. However, we have obtained products from resins obtained by use of an alkaline catalyst which were just as satisfactory as those obtained employing acid catalysts. Sometimes a combination of both types of catalysts is used in different stages of resinification. Resins so obtainedare also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. e., those referred to as highstage resins, are conveniently obtained by subjecting lower molecular weight resins to vacuum distillation and heating. Although such procedure sometimes removes only a modest amount or even perhaps no low polymer, yet it is almost certain to produce further polymerization. For instance, acid catalyzed resins obtained in the usual manner and having a molecular weight indicating' the presence of approximately 4 phenolic units or there-abouts may be subjected to such treatment, with the result that one obtains a resin having approximately double this molecular weight. The usual procedure is to use a secondary step, heating the resin in the presence or absence of an inert gas, including steam, or by use of vacuum.

We have found that under the usual conditions of resinification employing phenols of the kind here described, there is little or no tendency to form binuclear compounds, i. e., dimers, resulting from the combination, for example, of 2 moles of a phenol and one mole of formaldehyde, particularly where the substituent has 4 or 5 carbon atoms. Where the number of carbon atoms in a substituent approximates the upper limit specified herein, there may be some tendency to dimerization. The usual procedure to obtaina dimer involves an enormously large excess' of the phenol, for instance, 8 to 10 moles per mole of aldehyde. Substituted dihydroxydiphenylmethanes obtained from substituted phenols are not resins as that term is used herein.

Although any conventional procedure ordinarily employedm'ay be used in the manufacture of the herein contemplated resins or, for that matter, such resins may be purchased in the open market, we have found it particularly desirable to use the. procedures described elsewhere herein, and employing a combination of an organic sulfoacidand a mineral acid as a catalyst, and xylene as a solvent. By way of illustration, certain subsequent exmples are included, .but it is to be understood the herein described invention is not concerned with the resinsper se or with any particular method of manufacture but is concerned with the use of reactants obtained by the subsequent oxyalkylation thereof. The phenol-aldehyde resins may be prepared in any suitable manner.

Oxyalkylation, particularly 1 oxyethylation which is the preferred reaction, depends on contact between a non-gaseous phase and a gaseous pha e. It can, for example,'be carried out by melting the thermoplastic resin'and subjecting it to treatment with ethylene oxide or the like, or by treating a suitable solution or suspension. Since the melting points of the resins are often higher than desired in the initial stage of oxyethylation, we have found it advantageous to use a solution or su pension of thermoplastic resin in an inert solvent such as xylene. Under such circumstances, the resin obtained in the usual manner is dissolved by heating in xylene under a reflux condenser or in any other suitable manner. Since xylene or an equivalent inert solvent is present or may be present'during oxyalkylation, it is obvious there is no objection to having a solvent present during the resinifying stage if, in addition to beingjnert towards the resin,

it is also inert towards the reactants'and also inert towards water. Numerous solvents, particularly of aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, cymene, ethyl-"benzene,

vpropyl benzene, mesitylene, decalin, decahydronaphthalene), tetrain (tetrahydronaphthalene) ethylene glycol I diethylether, diethylene glycol diethylether, and tetraethylene glycol dimethylether, or mixtures of one or more. Solventssuch as dichloroethylether, or dichloropropylether may be employed either alone or in mixture but have the objection that the chlorine atom in the compound may slowly combine with the alkaline catalyst employed in oxyethylation. Suitable.

solvents may be selected from this group for molecular weight determinations.

The use of such solvents is a, convenient expedient in the manufacture of the thermoplastic resins, particularly since the solvent. gives a more liquid reaction mass and thus prevents overheating, and also because the solvent can be employed in connection with a" reflux condenser and a water trap to assist in the removal of water of reaction and also water present as part of the formaldehyde reactant when an aqueous solution of formaldehyde is used. .Such aqueous solution, of course, with the ordinary product of commerce containing about It'l to.40% formaldehyde, is the preferred reactant; When such solvent is used it is advantageously added at the beginning of the resinification procedure or.before the reaction has proceededvery far.

The solvent can be removed afterwards by distillation with or without the uselof vacuum, and a final higher temperature can be employed to complete reaction if desired., In many instances it is most desirableto permit part of the solvent, particularly when it is--i nexpensive,-e. g., xylene, to remain behind in a predetermined amount so as to have a resin which canbe handled more conveniently in the oxyalkylation stage. If a more expensive solvent, such as decalin, is employed, xylene or other inexpensive solvent may be added after the removal of decalin, if desired.

In preparing resins from difunctional phenols it is common to employ reactants of technical grade. The substituted phenols herein contemplated are usually derived from hydroxybenzene. As a rule, such substituted phenols are comparatively free from unsubstituted phenol. We have generally found that the amount present is considerably less than 1% and not infrequently in tual cross-linking, if it takes place even infrequently, must not be sufiicient to cause insolubility at the completion of the resinification stage or the lack of hydrophile properties at the completion of the oxyalkylation stage.

The exclusion of such trifunction phenols as hydroxybenzene or metacresol is not based on the fact that the mere random or occasional inlusion of an unsubstitued phenyl nucleus in the resin molecule or in one of several molecules, for example, markedly alters the characteristics of theoxyalkylated derivative. The presence of a phenyl radical having a reactive hydrogen atom available or having a hydroxymethylol or a substituted hydroxymethylol group present is a potential source of cross-linking either during resinification or oxyalkylation. Cross-linking leads either to insoluble resins or to non-hydrophilic products resulting from the oxyalkylatio procedure. With this rationale understood, it is obvious that trifunctional phenols are tolerable only in a minor proportion and should not be present to the extent thatinsolubility is produced in the resins, or that the product resulting from oxyalkylation is gelatinous, rubbery, or at least a not hydrophile. As to the rationale of resinification, note particularly what is said hereafter in differentiating between resoles, Novolaks, and resins obtained solely from difunctional phenols.

Previous reference has been made to the fact that fusible organic solvent-soluble resins are usually linear but may be cyclic. Such more complicated structure may be formed, particularly if a resin prepared in the usual manner is converted into a higher stage resin by heat treatment in vacuum as previously mentioned. This again is a reason for avoiding any opportunity for cross-linking due to the presence of any appreciable amount of trifunctional phenol. In other words, the presence of such reactant may cause cross-linking in a conventional resinification procedure, or in the oxyalkylation procedure,-

or in the heat and Vacuum treatment if it is employed as part of resin manufacture.

Our routine procedure in examining a phenol for suitability for preparing intermediates to be used in practicing the invention is to prepare a resin employing formaldehyde in excess (1.2 moles of formaldehyde per mole of phenol) and using an acid catalyst in the manner described in Example 1a of our Patent 2,499,370, granted March 7,1950. If the resin so obtained is solventsoluble in any one of the aromatic or other solvents previously referred to, it is then subjected to oxyethylation. During oxyethylation a temperature is employed of approximately to C. with addition of at least 2 and advantageously up to 5 moles of ethylene oxide per phenolic hydroxyl. V The oxyethylation is advantageously conducted so as to require from a few minutes up to 5 to 10 hours. If the product so obtained is solvent-soluble and self-dispersing or 11 emulsifiable, or has emulsifying properties, the phenol is perfectly satisfactory from the standpoint of trifunctional phenol content; The solvent may be removed prior to the 'dispersibility or emulsifiability test. When a product becomes rubbery during oxyalkylation due to the presence of a small amount of trireactive phenol, as previously mentioned, or for some other reason, it may become extremely insoluble, and no longer qualifies as being hydrophile as herein specified. Increasing the size of the aldehydic nucleous, for instance using heptaldehyde instead of formaldehyde, increases tolerance for trifunctional phenol.

The presence of a trifunctional or tetrafunctional phenol (such as resorcinol or bisphenol A) is apt to produce detectable cross-linking and insolubilization but will not necessarily do" so, especially .if the proportion is small. R'esinification involving difunctional phenols only may also produce insolubilization, although this seems to be an anomaly or a contradiction of What is sometimessaid in regard to resinification reactions involving difunctional phenols only. This is presumably due to cross-linking. This appears to be i contradictory to what one might expect in light of the theor of functionality in resinification. It is true that under ordinary circumstances, or rather under the circumstances of conventional resin manufacture, the procedures employing difunctional phenols are very apt to, and almost invariably do, yield solvent-soluble, fusible resins. However, when conventional rocedures are employed in connection with resins for varnish manufacture or the like, there is involved the matter of color, solubility in oil, etc. When resins of the same type are manufactured for the herein contemplated purpose, i. e., as a raw material to be subjected to oxyalkylation, such criteria of selection are no longer pertinent. Stated another way, one may use more drastic conditions of resiniflcation than those ordinarily employed to produce resins for the present purposes. Such more drastic conditions of resinification may include increased amounts of catalyst, higher temperatures, longer time of reaction, subsequent reaction involving heat alone or in combination with vacuum, etc. Therefore, one is not only concerned with the resinification reactions which yield the bulk of ordinary resins fromdifunctional phenols but also and particularly with the minor reactions of ordinary resin manufacture which are of importance in the present invention for the reason that they occur under more drastic conditions of resinification which may be employed advantageously at times, and they may lead to cross-linking.

In this connection it may be well to point out that part of these reactions are now understood or explainable to a greater or lesser degree in light of a most recent investigation. Reference is made to the researches of Zinke and his co-workers, Hultzsch and his associates, and to von Eulen and his co-Workers, and others. As to a bibliography of such investigations, see Carswell, r

for the time that sucl i're'simlat least under certain'circumstances, is susceptible to further complications.' Subsequently in the text it will be pointed out that cross-linking or reaction with excess formaldehyde may take place'even with one of such most typical type resins. This point is made for the reason that insolubles must be avoided in order to obtain the products herein but such addition to a 'Novolak causes cross-linking by virtue of the available third functional position.

' What has been said immediately preceding is subject to" modification in this respect: It is well knoWn, -for example, that difunctional phenols, for instance, paratertiaryamylphenol, and an aldehyde, particularly formaldehyde, may yield heat-hardenable resins, at least under certain conditions, as for example the use of two moles of formaldehyde to one of phenol, along with an alkaline catalyst. This peculiar hardening or curing or cross linking of resins obtained from difunctional phenols has been recognized by various authorities.

The intermediates-herein used must be hydro- ;phile or 'sub' surface-active or surface-active as hereinafter described, and this precludes the form'ation of insolubles during resin manufacture or the'subsequent stage of resin manufacture where heat alone, or heat and vacuum, are employed, or in the oxyalkylation procedure. In its simplest presentation the'rationale'bf' resini'fication involvin'g formaldehyde, for example, and a difunctional phenol would not be 'expected'to form "cross-links] However, cross-linking sometimes occurs and it may reach the objectionable stage. However, provided that the preparation of resins simply takes'int'o cognizance the present knowledge of the subject, and employing preliminary, exploratory routine examinations'as' herein in dicated, there is not the slightest difliculty in preparing a very large'number of resins of various types and from various reactants, and by means of different catalysts by different procedures, all of which are eminently suitable for the herein described purpose.

Now returning to the thought that cross-linking can take place, even when difunctional phenols are" used exclusively, attention is directed to the following: Somewhere'd'uring the course of resin manufacture there maybe a potential cross-linking combination formed but actual cross-linking may not take place until the subsequent stage is reached, 1. e., heat and vacuum stage, or oxyalkylation stage. This situation may be related or explained in terms of a't'heory of .fiaws, or Lockerstellen, which is employed in explaining flaw-forming groups due' to the fact that a 'CHzOH radical and H atom may'not lie the same plane in the'manufacture of ordinary phenol-aldehyde"resins.

Secondly, the formation or absence of formamation of insolubles'may be related to the aldehyd'e used and the ratio of aldehyde, particularly amps? i3 formaldehyde. insofar that a: slight" variation may, under circumstances not understandable, produceinsolubilization; The formation of the insoluble resin is apparently very sensitive to the quantity of formaldehyde employed and a slight increase in'tlie proportion of formaldehyde may lead to the formation of insoluble gel lumps. The cause of insoluble resin formation is not clear, and nothing is known as to the structure of th'ese'resins.

N All that has been said previously herein as regards resinification has avoided the specific reference to activity of a methylene hydrogen atom; Actually there is a possibility that under some drastic 'conditionscross-linking may take place through formaldehyde addition to the methylene bridge, or some other reaction involving a methylene atom, i a

Finally, jthere is some evidence that, although thefmeta" positions are not own-tarry reactive, possibly at times methylol groups or the like are formed at the meta positions? and if this were the ease'it may be a suitable explanation ofabnormal cross-linking. l

Reactivity of a resin towards excess aldehyde, for instance formaldehydais not to be taken as a criterion of rejection for use asja reactant. In

other words, a plienol-aldehyde'resin which is thermoplastic and solvent-"soluble, particularly if xylene-soluble lis perfectly satisfactory even though retreatmenfiwitl'i more aldehyde may change its characteristics markedly in "regard to both fusibilityand solubility. Stated another 'wayifasfar as resinsobt'ained from difunctional phenols are concerned, they may beeither formaldehyde-resistant or not formaldehyde-resis'ta'nt. i

Referring again to the resins herein contemplated as reactants, "it is to be'noted that they are thermoplastic phenol-aldehyde resins derivedfrom difunctional phenols and are clearly distinguished fromNbvolaks or resoles. When these resins are produced from difunctional phenols and some of the higher aliphatic aldehydes'; such as .acetaldehyde, the resultant is often a comparatively soft or. pitchlike resin at ordinary temperature. "Such resins become com-.-

paratively fluid at to C; as a rule and thus can be readilyloxyalkylated, preferably oxyethylate'd, without' the use ofa solvent.

Reference has been made toitheuse of the wordfusibl'e. Ordinarily a thermoplastic resin isidei'itified asone which'can be heated repeatedly and still-not lose its thermoplasticity.

It is recognized, however, that 'one may havea 4 resin'which is initially thermoplastic but on rep'ea'ted heatingmay become insoluble in an organic solvent, or at least no longer thermoplastic, due to' the fact that certain changes take place very slowly. As far as the "present'inven tion is concernedit is obvious that a resin to be suitable need only be sufficiently fusible to per mit processing to produce our oxyalkylat'ed products and not yield insolubles or cause irisolubilization or gel. formation; "or 'rubberiness; as 'pre- 'viously described. Thus'resins which are, strictly The properties. Ihe hydrophile propertyis in trddueedby"fxyalkylatiqn; In the hereto a'ppended claims and elsewherefthe' expression" ivater-insoluble "is usedto point out this char'- acteristic of the resins used. 7 a

the manufacture of compounds herein employed, particularly for demulsification, it is obvi us th'at the r sins ran be obtained by one of ahiiifiber of 'p'rocedur'es. In the 'first'place, suit able resins are marketed by a'number ofcom panics-"and can be purchased'in the open market; inthesecend place, there area wealth of ex-' amples of suitable resins described in the literatiire Tlietliird procedure is to follow the 'directinsie'f thepresent"application.

The polyhydric' reactants, i. e., the oxyalkyla tion sus'ceptibIe, water-insoluble, organic solvent-' soluble, fusible; phenol-aldehyde resins derived from difunctional phenols, used" as intermediates t6 produce the products used in accordance with th invention, are exeinp'lifi'ed by Examples 'Nosl Id through 103d of our Patent 2,499,370, granted Maren-7,1959, 'and' ref erenceis made't'dthat patefit'for examples of the 'oxyalkylated resins us as memediates;

*lre ous 'r'efereiice'has'been made to the use of a single phenol as herein specified, "or asing'le' reattwiaiahyde; 61 a single'oxyalkylating agent. Obviously}: mixtures of reactantsfifray "'be em ployed, asjfoi' example ajmixtur "bf para butylphenol "and Tpara-afnylplienohor" a mixture of para-butylpnenol and para-hexylphenol; or parabutylphenolfa'nd para pli'nylphenol. It is extremelydiffi'cult to depict thestructur'e of a'resi'n' derivedfrorn a singlephenoll When mixtures of phenols are used, even in equimolar proportions; thestructure'of the resin; is even more indeterfn fiableTTn other words," a'mixture involving butylphen'ol "an para amylphenol might an alternation of the two 'nuclei'or one havea'senes of'butylatednuclei and then a'series ofamylated nuclei. If a mixture of aldehy desis'employed, for instance, acetaldehyde and butyraldehyde, 'or acetaldehyde and formaldehyde, or benzaldehyde and acetaldehyde, the final structure of the resin becomes even more complicated"andpossibly depends on the relative re tivity of the aldehydes. For that matter, one

' i" PARTZ Having obtained a suitable resin of the kind 'describedf 'such resin is subjected to treatment with a low molal reactive alpha-beta olefin oxide so'as to render the product distinctly hydrophile iiinatureas indicated by the fact that it'becomes self-erriulsifiable or lmiscibleor soluble in water, orself-dispersible, or has emulsifying properties. The olefin'oxides employed are characterized by ang es? the ,fact that they contain not over ,4 .carbon atoms and are selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide. glycide, and methylglycide. Glycide may be, of course, considered as a hydroxy propylene oxide and methyl glycide as a hydroxy butyleneoxide. In any event, however, all such reactants contain the reactive ethylene oxide ring and may be best considered as derivatives of or substituted ethylene oxides. The solubilizing effect of the oxide is directly proportional to the percentage of oxygen present, or specifically, to the oxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methyl glycide, 1:2. In such compounds, the ratio is very favorable to the production of hydrophile or surfac..- active properties. However, the ratio, in propylene oxide, is 1:3, and in butylene oxide, 1:4. Obviously, such latter two reactants are satisfactorily employed only where the resin composition is such as to make incorporation of the desired property practical. In other cases, they may produce marginally satisfactiry derivatives, or even unsatisfactory derivatives; They are usable in conjunction with the three more favorable alkylene oxides in all cases. For instance, after one or several propylene oxide or butylene oxide molecules have been attached to the resin mole cule, oxyalkylation may be satisfactorily continued using the morefavorable members of the class, to produce the desired hydrophileproduct. Usedalone, these two reagents may in some cases fail to producesufficiently hydrophile derivatives because of their relatively low oxygen-carbon ratios.

Thus, ethylene oxide is much more effective than propylene oxide, and propylene oxide is moreeffective than butylene oxide. Hydroxy propylene oxide (glycide) ismore effective than propylene oxide. Similarly, hydroxy butylene oxide (methyl glycide) is more effective than butylene oxide. Since ethylene oxide is the cheapest alkylene oxide available and is reactive, its use is definitely advantageous, and especially in light of its high oxygen content. Propylene oxide is less reactive than ethylene oxide, and butylene oxide is definitely less reactive than propylene oxide. On the other hand, glycide may react with almost explosive violence and must be handled with extreme care.

The oxyalkylation of resins of the kind from which the initial reactants used in the practice of the present invention are prepared is advantageously catalyzed by the presence of an alkali. Useful alkaline catalysts include soaps, sodium acetate, sodium hydroxide, sodium methylate, caustic potash, etc. The amount of alkaline catalyst usually is between 0.2% to 2%. The temperature employed may vary from room temperature to as high as 200 C. The reaction may be conducted with or without pressure, i. e., from zero pressure to approximately 200 or even 300 pounds gauge pressure (pounds per square inch). In a general way, the method employed is substantially the same procedure as used for oxyalkylation of other organic materials having reactive phenolic groups.

It may be necessary to allow for the acidity of a resin in determining the amount of alkaline catalyst to be added in oxyalkylation. For instance, if a nonvolatile strong acid such .as sulfuric acid is used to catalyze the resinification reaction, presumably after being converted "into a sulionic acid, it. may be necessary andis usually 16 advanta ou t a a am un f ellseli i e stoichiometrically to such acidity, and include added alkali over and above this amount as the alxaline c atalyst.

Itis advantageous toconductthe oxyethylation in presencepf an inert solvent such as xylene, cyn' ene, decalin, ethylene glycol diethylether, diethyleneglycol diethylether, or the like, although with many resins, the oxyalkylation proceeds satisfactorily without a solvent. Since xylene is cheap and may be permitted to be present in the final product used as a demulsifier, it is our preferenceto use Xylene. This is particularly true in the manufacture of products from low-stage resins, i. e., of 3 and upto and including 7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated, the pressure readings of course represent total pressure, that is, the combined pressure due to xylene and also due to ethylene oxide or whatever other oxyalkylating agent is used. Under such circumstances it may benecessary at times to use substantialpressures to obtain effective results, for instance, pressures up to 300 pounds along with correspondingly high temperatures, if required.

However, even in the instance of highmelting resins, a solvent such as xylene can be eliminated in either one of two ways: After the introduction of aproximately 2or 3 moles of ethylene oxide, for example, per phenolic nucleus, there is a definite drop in the hardness and melting point of the resin. At this stage, if xylene or a similarsolvent has been added, it can be eliminated by distillation (vacuum distillation if desired) and the subsequent intermediate, being comparatively soft and solvent-free, can be reactedfurther in the usual manner with ethylene oxide orsorne other suitable reactant.

Another procedure is to continue the reaction tocompletion with such solvent present and then eliminate the solvent by distillation in the customary manner.

Another suitable procedure is to use.propylene oxide or butylene oxide as a solvent as well'as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the powdered resin inpropyle'ne'oxide even though oxyalkylation is taking place to a greateror lesser degree. Afte a solution has been obtained which representsthepriginal resin dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated productfethylene oxide isadded to react with'th'e liquid mass until hydrophile properties are obtained. Since ethylene oxide is more reactive than propylene oxide or butyleneoxide; the final product may contain someiunreacted propylene oxide or butyleneoxide which can be eliminated by volatiliz'ation or distillation in any suitable manner. I

Attention is directed to the fact that the resins herein described must be fusible or soluble in an organic solvent. ,Fusible resins invariably are solublein one or more organic solvents such as those mentioned'elsewhere herein. It is to be emphasized, however, that the organic solvent employedto indicate or assure that the resin meets this requirement need not be the one used in oxyalkylation, Indeed, solvents which are susceptible to oxyalkylation are included in this group of organic solvents. Examples of such solvents are alcohols and alcohol-esters. However, Where a resin is soluble in an organic solvent, there are usually available other organic solvents whichare. not susceptible to oxyalkylation, useful l9 tence as a rule through the presence of a surface-active emulsifying agent. Some surfaceactive emulsifying agents such as mahogany soap may produce a water-in-oil emulsion or an oilin-water emulsion depending upon the ratio of the two phases, degree of agitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of Water and shaken to produce an emulsion. The amount of xylene is invariably sufficient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-inwater type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly, in the lowest stage of oxyalkylation, one may obtain a waterin-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with water.

- If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 units per that such mixture, or any other similar mixture, "is considered the equivalent of xylene for the purpose of this test. In many cases, there is no doubt as to the presence or absence of hydrophile or surface-active characteristics in the polyhydric reactants used in accordance with this invention.

They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surfaceactive property (sub-surface-activity) tests for emulsifying properties or self-dispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus. 1

The presence of xylene or an equivalent waterinsoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approximate point where self-emulsification begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylenefree resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It is to .be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with Water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in'oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

In light of what has been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the eiiectiveness of various alkylene oxides, and most particularly all ethylene oxide, to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide employed, as long as it is at least 2 moles per phenolic nucleus, for producing products useful for the practice of this invention. Another variation is the molecular size of the resin chain resulting from reaction between the difunctional phenol and the aldehyde such as formaldehyde. It is well known that the size and nature or structure of the resin polymer obtained varies somewhat with the conditions of reaction, the proportions of reactants, the nature of the catalyst, etc.

Based on molecular weight determinations, most of the resins prepared as herein described, particularly in the absence of a secondary heating step, contain 3 to 6 or 7 phenolic nuclei with approximately 4 or 5 nuclei as an average. More drastic conditions of resinification yield resins of greater chain length. Such more intensive resinification is a conventional procedure and may be employed if desired. Molecular weight, of course, is measured by any suitable I procedure, particularly by cryoscopic methods; but using the same reactants and using more drastic conditions of resinification one usually finds that higher molecular weights are indicated by higher melting points of the resins and. a tendency to decreased solubility. See what has been said elsewhere herein in regard to a secondary step involving the heating of a resin with or without the use of vacuum.

We have previously pointed out that either an alkaline or acid catalyst is advantageously used in preparing the resin. A combination of cata-lysts is sometimes used in two stages; for instance, an alkaline catalyst is sometimes employed in a first stage, followed by neutralization and addition of a small amount of acid catalyst in a second stage. It is generally believed that even in the presence of an alkaline catalyst, the number of moles of aldehyde, such as formaldehyde, must be greater than the moles of phenol employed in order to introduce methylol groups in the intermediate stage. There is no indication that such groups appear in the final resin if prepared by the use of an acid catalyst. It is possible that such groups may appear in thefinished resins prepared solely with an alkaline catalyst; but we have never been able to confirm this fact in an examination of a large number of resins prepared by ourselves. Our preference, however,

:a ultimte-m xim Onesh underestimate the utility of any of these ap Impound; len

stanc h ys mple: rul :.to;;.fo1low is :EIfip n s xesimhavin n i-l ast th eeph lic nuclei and being organic 1splvent-s01llble'. Qxyethylate suchresin usingthe following four ratios of moles of ethylene oxide perephenolicwunit.equivalent: 2 to 1; 6 to 1; 10 to 1; and to 1. From a sample of each product remove any solvent that may be present, such as xylene. Prepare 0.5% and 5.0% solutions in'distilled water, as previously indicated. A mere egamination gf such series will generally reveahan-approximate range of minimum hydrophile character; moderate hydrophile character, and maximum hydrophile character. If the 2 to 1 ratio does not show minimum hydrophile oharactenloy @stgfjhe solvent-free product, then one should-test its capacity to form an emulsion when admixed with Xylene or other insoluble solvent. If neither test ShOWs the requi e mi imu r p le; p q e ty, repe it n usin oto. 4.,m0lfls per phenolic nucleus will e ve. Moder tehydrophflech ra te ho l. be s n b th r-t e 6 to .l o 0-t0.,.1,ratio- -Sue mod r te drcn l cha act in cat d :by hetac th the s ei t led wate hin th p vi u y mentioned co entretion ran e onl e ma n t ns e 91- when view di ammparat vely: t in .lave w r in anc the de th o btai iabl- {Tile t-With bntyl- Q ides 91 5 s s quen ae at s epmi eead r e ethylene oxigle. o

2/2, e uequslu n is ha e v i-'=-a ex n l est for; s ri ce, a t it r v u e er ncep es been madet x ith tplhe ox al l ti -fi u. a r i ..;the';:u.s .;q increa ed; -Qi

i'siechd alkylene ;o ic1 t ow v rlzi one doe involvecl-- an i imsue keme emssui smt s in l e-.7 wher e amp esusin ap rox ma e y t 01% -y we eh ..,;e at i e am l usine'a q 590% to 7 0%.;byyve sht, t. ;.-.exp er the a ihvdsophile-hydrophobe balance.

Arp actioal. examinat on-gof-ethe factor ntroxw alkylatiqnlevelcan bemade, by a very simpletest using a pilot plant autoclave havinga;capaci ty of alkylate. ltpret raplyy. ewethyletedmvitheu xth about ii 1. 1:01.115; allons as.- hereinaften describedgofeasolvent. such-laboratoryepreparedimutine compqundscan m fe c em mngeh -i h mb re n then be tested for solubility and, generally speaking, this is all that is required to give a suitable variety covering the hydrophile-hydrophobe range. All these tests, as stated, are intended to be routine tests and nothing more. They are intended to teach a person, even though unskilled in oxyethylation or oxyalkylation, how to prepare in a perfectly arbitrary manner, a series of compounds illustrating the hydrophile-hydrophobe range.

If one purchases a thermoplastic or fusible resin on the open market selected from a suitable number which are available, one might have to make certain determinations in order to make the quickest approach to the appropriate oxyalkylation range. For instance, one should know (a) the molecular size, indicating the number of phenolic units; (17) the nature of the aldehydic residue, which is usually CH2; and (c) the nature of the substituent, which is usually butyl, amyl, or phenyl. With such information one is in substantially the same position as if one had personally made the resin prior to oxyethylation.

For instance, the molecular weight of the internal structural units of the resin of the following over-simplified formula:

H OH OH H r H -o- -o H H R R n R (n=1 to 13. or even more) is given approximately by the formula: (mol. weight of phenol -2) plus mol. weight of methylene or substituted methylene radical. The molecular weight of the resin would be n times the value for the internal limit plus the values hand terminal unit lacks the methylene bridge element. Using one internal unit of a resin as the basic element, a resins molecular weight is given approximately by taking (1L plus 2) times the weight of the internal element. Where the resin molecule has only 3 phenolic nuclei as in the 7 structure shown, this calculation will be in error by several per cent; but as it grows larger, to contain 6, 9, or 12 phenolic nuclei, the formula comes to be more than satisfactory. Using such an approximate weight, one need only introduce, for example, two molal weights of ethylene oxide or slightly more, per phenolic nucleus, to produce a product of minimal hydrophile character. Further oxyalkylation gives enhanced hydrophile character. Although we have prepared and tested a large number of oxyethylated products of the type described herein, we have found no in stance where the use of less than 2 moles of ethylene oxide per phenolic nucleus gave desirable products.

- Examples 11) through 182), and the tables which appear in columns 51 through 56 of our said Patent 2,499,370 illustrate oxyalkylation products from resins which are useful as intermediates for producing the esterified products used in aciii) cordance with the present application, such ex amples giving exact and complete details for carrying out the oxyalkylation procedure. The resins, prior to oxyalkylation, vary from tacky, viscous liquids to hard, high-melting solids. Their color varies from a light yellow through amber, to a deep red or even almost black. In the manufacture of resins, particularly hard resins, as the reaction progresses the reaction mass frequently goes through a liquid state to a sub-resinous or semi-resinous state, often characterized by being tacky or sticky, to a final complete resin. As the resin is subjected to oxyalkyla tion these same physical changes tend to take place in reverse. If one starts with a'solid resin, oxyalkylation tends to make it tacky or semiresinous and further oxyalkylation makes the tackiness disappear and changes the-productto' a liquid. Thus, as the resin is oxyalkylated it decreases in viscosity, that is, becomes more liquid or changes from a solid to a liquid, particularly when it is converted to the water-dispersible or water-soluble stage. The color of the oxyalkylated derivative is usually considerably lighter than the original product from which it is made, varying from a pale straw colorto an amber or reddish amber. The viscosity usually varies from that of an oil, like castor oil, to that of a thick viscous sirup. Some products are waxy. The presence of a solvent, such as 15% xylene or the like, thins the viscosity considerably and also reduces the color dilution. No undue significance need be attached to the color for the reason that if the same compound is prepared in glass and in iron, the latter usually has somewhat darker color. If the resins are prepared'as customarily employed in varnish resin manufacture, i. e., a procedure that excludes the presence of oxygen during the resinification and subsequent cooling of the resin, then of course the initial resin is much lighter in color. We have employed some resins which initially are almost waterwhite and also yield a lighter colored final product. Actually, in "considering the ratio of alkylene oxide to add, and we have previously pointed out that this can be pro-determined using laboratory tests, it is our actual preference from a practical standpoint to make tests on a small pilot plant scale. Our reason for so doing is that We make one run, and only one, and that we have a com plete series which shows the progressive effect of introducing the oxyalkylating agent, for instance, the ethyleneoxy radicals. Our preferred pro: cedure is as follows: We prepare a suitable resin, or for that matter, purchase it in the open market. We employ 8 pounds of resin and 4 pounds of xylene and place the resin and xylene in a suitable autoclave with an open reflux condenser. We prefer to heat and stir until the solution is complete. We have pointed out that softresins which are fluid or semi-fluid can be readily prepared in various ways, such as the use of ortho-tertiary amylphenol, ortho-hydroxydiphenyl, ortho-decylphenol, or by the use of higher molecular weight aldehydes than form-' aldehyde. If such resins'are used, a solvent need not be added but may be added as a matter-of convenience or for comparison, if desired We then add a catalyst, for instance, 2% of caustic soda, in the form of a 20% to 30% solution, and remove the water of solution or formation. We then shut oif the reflux condenser and use the equipment as an autoclave only, and oxyethylate until a total of 60 pounds of ethylene oxide have ate-later of about 150 Q. at intermediate" $51 55 W? t fs mi e point's' asindicated in the following table:

Pounds of Ethylene Percentages Oxide Added per 8-pound Batch;

' for' iii' stance, 2 "to 4"oun'ces, so that no corfectlon-need be' m'adein regardte;the reeid al raetion mass-i interfac or aliiiiiid-lifiifid'interface: If desired, surface activity can I be etsarea' in any one of D NOUYihiOfiltFQl dropping pipe tte, or "a other procedure for riie'as'uring interment tension. sue}; testsare nvie a j alia d Any-compound-hayin ub -fuither ds'ription. jr'ra'aeway; and Sm and diyaikylatgq t6 'a -ratef *xtent hose-hayinga fgreater proportionof alltyleri re" useful aspo w hydric i reactants for the" practice-of this inventinu- Another rea an hyweprerr to use afpilot plantites't of the kfind aboye'described tbat we l; canusethe saiiiepmbedure to eyaluat tolerance towa'r s'a*trifunctionalfphenol such ashydroxY-j w i im i xtefi w f 3 1 0 6rubb nltha flep "ee l ti wbvi u t. ur'e" of evaluating trifuir'ictio eis more suitable than the pre i ous procedure.

It may be well to call attention to one result which may be noted in a long drawn-out oxyalkylation, particularly oxyethylation, which would not appear in a normally conducted reaction. R eference has been made to cross-linking and its efiect 0n solubility and also the fact thatj i'f' carried far enough, it ceases inifiiefi't stringinss, then faiiaunea stringin s', usually followed by a semi-rubbery or rubbery stage. Incipient stringiness, or even prononuced stringiness, or even the tendency toward a. rubbery stage, is not objectionable so long as the final product is still hydrophile and at leas iid ksm m'ifihe ake place iatall} ammaeqmme 1, area-w n? of res'fiis tree-ta W1 h "n equal weight ofyor a?" '1 "ht; oiyethylenef oxide; Thi s may bejdon comparatiy'ly short tirne,'for 1 1 st cifatfl50br l lljic irr 4'to8 hours, or; e; le arid; an exploratory-1 ac nd oreviqu's'li describedjthe 5 t added extremely slowlyin mples, so that 'th'efra'f tinies 16mg to "intro uce mount 6 ethylene oxide efnployirlg *praturituen ethrifioa'tion might in ness'or a ugges'ti o'n of rubberines'sj rr if'i nexpl 'ra'torygexperimem; previously described there ppears t ngi nes's "rubberines's, it may be "e kfierlr'iient' aiid reahth inge of okyalkylation :as rapidly as 'en proceed slowly beyond this in-" Theentir purpose of this but down the timeof re:

ticres ri ha's' be'eiro'xy ethylatedj until" it the following way where 811 is a fairly large num-. her, for instance, to 20, decomposes and an oxyalkylated resin representing a lower degree of oxyethylation and a less soluble one, is generated and a cyclic polymer of ethylene oxide is produced, indicated thus:

Him

This fact, of course, presents no difiiculty for the reason that oxyalkylation can be conducted in each instance stepwise, or at a gradual rate, and samples taken at short intervals so as to arrive at a point where optimum surface activity or hydrophile character is obtained if desired; for productsfor use as polyhydric reactants in the practice of this invention, this is not necessary and, in fact, may be undesirable, i. e., reduce the efliciency of the product.

. We do not know to what extent oxyalkylation produces uniform distribution in regard to phenolic hydroxyls present in the resin molecule. In some instances, of course, such distribution cannot be uniform for the reason that we have not specified that the molecules of ethylene oxide, for example, be added in multiples of the units present in the resin molecule. This may be illustrated in the following manner:

. Suppose the resin happens to have five phenolic nuclei. If a minimum of two moles of ethyl ene oxide per phenolic nucleus are added, this would mean an addition of 10 moles of ethylene oxide, but suppose that one added 11 moles of ethylene oxide, or 12, or 13, or 14 moles; obviously, even assuming the most uniform distribution possible, some of the polyethyleneoxy radicals would contain 3 ethyleneoxy units and some would contain 2. Therefore, it is impossible to specify uniform distribution in regard to the entrance of the ethylene oxide or other oxyalkylating agent. For that matter, if one were to introduce moles of ethylene oxide there is no way to be certain that all chains of ethyleneoxy units would have 5 units; there might be some having, for example, 4 and 6 units, or for that matter 3 or 7 units. Nor is there any basis for assuming that the number of molecules of the oxyalkylating agent added to each of the molecules of the resin is the same, or different. Thus, where formulae are given to illustrate or depict the oxyalkylated products, distributions of radicals indicated are to be statistically taken. We have, however, included specific directions and specifications in regard to the total amount of ethylene oxide, or total amount of any other oxyalkylating agent, to add.

In regard to solubility of the resins and the oxyalkylated compounds, and for that matter derivatives of the latter, thefollowing should be noted. In oxyalkylation, any solvent'employed should be non-reactive to the alkylene oxide employed. This limitation does not apply to scl-' vents used in cryoscopic determinations for ob-v vious reasons. Attention is directedv to the fact 28 that various organic solvents maybe employed to verify that the resin is organic solvent-soluble. Such solubility test merely characterizes the resin. The particular solvent used in such test may not be suitable for a molecular weight determination and, likewise, the solvent used in determining molecular weight may not be suitable as a solvent during oxyalkylation. For solution of the" oxyalkylated compounds, or their derivatives a great variety of solvents may be employed, such as alcohols, ether alcohols, cresols, phenols, ketones, esters, etc., alone or with the addition of water. Some of these are mentioned hereafter. We prefer the use of benzene or diphenylamine as, a solvent in making cryoscopic measurements. The most satisfactory resins are those which are soluble in xylene or the like, rather than those which are soluble only in some other solvent containing elements other than carbonand hydrogen, for instance, oxygen or chlorine; Such solvents are usually polar, semi-polar, or slightly polar in nature compared with xylene, cymene, etc.

Reference to cryoscopic measurement is concernedwith the use of benzene or other suitable compound as a solvent. Such method will show that conventional resins obtained, for example, from para-tertiary amylphenol and formaldehyde in presence of,an acid catalyst, will have a molecular weight indicating 3, 4, 5 or somewhat greater number of structural units per molecule. Ifmore drastic conditions of resinification are employed or if such low-stage resin is subjected to a vacuum distillation treatment as previously described, one obtains a resin of a distinctly higher molecular weight. Any molecular weight determination used, whether cryoscopic measurement or otherwise, other than the conventional cryoscopic one employing benzene, should be checked so as to insure that it gives consistent values on such conventional resins as a control.

Frequently all that is necessary to make an under conditions to insure dimerization. As to the preparation of such dimers from substituted phenols, see Carswell, Phenoplasts, page 31.- The increased viscosity, resinous character, and decreased solubility, etc., of the higher polymers in comparison with the dimer, frequently are all that is required to establish that the resin contains. 3 or more structural units per molecule.

Ordinarily, the oxyalkylation is carried out in autoclaves provided with agitators or stirring devices. We have found that the speed of the agitation markedly influences the reaction time. In some cases, the change from slow speed agitation, for example, in a laboratory autoclave agitation with a stirrer operating at a speed of 60 to 200 2-9 R. P. M., to highspeed agitatien, withthestirrer operating at 250 to 350 R. P. M., reduces the time required for oxyalkylation by about one-half to toztwo-thirds. Frequently xylene-soluble prod-- ucts which give insoluble products 'by procedures employing comparatively slow speed agitation; give suitable hydrophile products when-produced by sirnilarspro edurebut with high .speedagitation, as a: result, we believe, of the reduction in the time required with consequent elimination. or curtailment of opportunity for curing or etherization. Even if the formation of; an inoluble product is notiinvolved, it is frequently advantageous to speed: up the reaction, thereby. reducing production time, by increasing agitating speed. In large scale operations, we have demonstrated that economical manufacturing results from continuous oxyalkylation, that:. is, an operation in which the alkylene oxide is continuously fed to the reaction vessel, with high speed agitation, i. e., an agitator operating: at 250130 35011112. M. Continuous.-oxyalkylation, other conditions being the same, is more rapid than batch oxyalkylation, but the latter is ordinarily more convenient for laboratory operation. Previous. reference hasbeen made to the fact that in. preparing esters or compounds of the kind herein described. particularly adapted for demulsification of water-in-oil emulsions, and for that matterafor other purposes, one should make a complete exploration of the wide variation in hydrophobe-hydrophile balance as previously -referred to.

meansvthatzone: employinga the present invention.

should take the choice or the most suitable de rivative selected from a number of representative compounds, thus, not only should a. variety of resinsbe prepared f exhibiting, a. variety of. oxyalkylations; particularly oxyethylations, but also a variety of derivatives. This can be done; conveniently in light of what has been said previously. From a practical standpoint, using pilot plant equipment, for instance, an autoclave having a capacity of approximately, three to. five gallons. We have made a single run by appropriate selections in which the molal ratio .of resin equivalent to ethylene oxide is one to one, 1 to 5, 1 to. 10, l. to 15,. and 1. to 20. Furthermore,.in making these particular runs we have used continuous addition of ethylene oxide. In the continuous addition of ethylene oxide we have emplo cd either a..cy1inder,.. of ethylene-oxide without added" nitrogen, provided that the pressure -of the ethylene oxide was sufiiciently great to pass into the autoclave, or elsegwe have used an arrangement which, in,. essence,..wes.the..equiv-- alent of an ethylene oxide cylinder with a means for injecting nitrogen so as to force :out the ethylene oxide in the manner of an ordinary seltzer bottle, combined with. the means for either weighing the cylinder or measuring the ethylene oxide -usedvolumetrically. Such -proeedure -andarrangement-forinjecting liquids is, or course; conventional. The following data sheets exempliiy such operations, i. e., the combination of bothcontinuous agitation and taking samples so as to give five different variants in oxyethylation. In adding ethylene oxide continuously, there is one precaution which must be taken at all times. The addition of ethylene oxide must stop immediately if there is any indication that not started at the beginning of the reaction pe riod. Since the addition of ethylene oxideisdnvariably an exothermic reaction, whetherrorxnot reaction has taken place' can be judged in the usual manner by; observing (a) temperature rise or drop, if any; (2)) amount of cooling water or other means required to dissipate heat of reaction; thus, it. there. is atemperature drop with- ;out the.use' of. cooling; water. or' equivalent, or if t e e is 1 0 r s in m era W thout usin investigation and then if ethylene oxide is added.slowly.;..this

temperature is maintained by co ling water until the oxyethylation is complete. Werhave also indicated .the'; maximum .pressure that we obtained or'the pressure range. Likewise, wehaveindiL- cated the time required to inject theoethylene oxide as well asa brief note as to the solubility of the product at the. end of the oxyethylation period. As' one period ends it willlbe rIotedJwe have removed part of the oxyethylated mass to give us derivatives, as therein described; the rest has beensubjected tofurther. treatment; All this is apparent by examining the columns headed Starting-mix, Mixat end of reaction,

'Mix which is =removed for sample, and Mix which remains as next starter.

The resins employed are prepared in the mannerdescribed in Examples 1a through 103a of our said Patent 2,499,370, except that instead of I being'prepared .on: a laboratory sc ale they were prepared in l0to '15-gallon electro-vapor-heated ynthetic. resin pilot plant reactors, as manufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, andcompletely described in their bulletin No. 2087 issuedin 1947, with specific reference-to Specification No. 71-3965.

taken at each stage, for instance. to" one gal- Ion, one can' proceed through the-entireimolail.

stage of 1 to 1, to 1 to 20, without. remaking at any intermediate stage. This is illustrated by Example 1055b.- In other examples we foundiit desirable to take a larger sample, for instance a; 3-gallon-sample, at an intermediate stage. As a result it -was necessary in" such instances to start with a new resin sample in order to prepare sufficient oxyethylated derivatives illustrating the latter stages. Under such circumstances, of course, the earlier stages which had been previously prepared were by-passed or ignored. This is illustrated in the table where, obviously, it shows that the starting mix was not removed from a previous sample.

Phenol for resinf Para-tertiary amylphenol Aldehyde for resin: Formaldehyde Date, June 22, 1948 [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 3a of Patent 2,499,370 but this batch designated 10411.]

Mix Which is Mix Which Re- Removed for mains as Next Sample Starter Max Time Pressure Temperahrs Solubility lbs. sq. in. ture, C.

Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs Lbs. Lbs. Lbs I 801- Res- Eto Sol- Res- Etc 801- Res- .Sol- Res- Eto Mix at End of Starting MiX Reaction' vent 1n vent in vent in vent in First Stage Resin'to EtO Molal Ratio 11.. Ex. No. 104b..

Second Stage Resin to Et0 Molal Ratio 125.. 10 9 Ex. N0. h...

Third Stage Resin to EtO.

Molal Ratio 1:10 Ex. No. 106b Fourth Stage Resin to EtO Molal Ratio 1:15. Ex. No. 107b- Fifth Stage Resin to Etouu} 7 9.94 7.13 7. 93 19.69 3.29 3.68 9.04 3.84 4.25 10.65 60 173 A) FS 3. 84 4.25 10.65 3. 84 4. 25 16. 15 2.04 2.21 8. 55 1.80 2.04 7.60 220 160 P5 RS Molal Ratio 1:20. Ex. No. l08b..

I=Insoluble. ST=S1ight tendency toward becoming soluble. FS=Fairly soluble. RS=Readily soluble. QS=Quite soluble.

Phenol for resin: Nonylphenol Aldehyde for resin: Formaldehyde Date, June 18, 1948 [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 70a of Patent 2,499,370 but this batch designated 109a.]

. Mix Which is Mix Which Re- Starting Mix figg ggg of Removed for mains as Next Sample Starter M ax Max Pressure Temperaag? Solubility I gbls. kbs. Lbs lbls. %bs. gbls. Ifibs. Lbs l b s. abs. Lbs

o eso teso eso esvent in Eto vent in Eto vent in Eto vent in Eto First Stage Resin to EtO Molal Ratio 1:1. l5 0 15. 0 0 15. 0 15. 0 3 5. 0 5. 0 1. 0 10. 0 10. 0 2. 0 50 150 1% ST Ex. No. 109b Second Stage Resin to EtO Molal Ratio 1:5 10 10 2.0 10 10 9.4 2. 72 2. 72 2. 56 7. 27 7. 27 6.86 100 147 2 D1 Ex. N0. b

Third Stage Resin to EtO Y Molal Ratio 1:10. 7. 27 7. 27 6. 86 7. 27 7. 27 13. 7 4.16 4. 16 7. 68 3. 15 3. 15 5.95 1% 8 Ex. N0. 111b.

Fourth Stage Resin to EtO. Molal Ratio 1:15. 3. 15 3. 15 5. 95 3.15 3.15 8.95 1.05 1.05 2. 95 2. 10 2.10 6.00 220 174 2% 8 Ex. No. 112b.

Filth Stage Resin to EtO-- Molal Ratio 1:20. 2.10 2.10 6.00 2.10 2.10 8.00 220 183 36 VS Ex. N0.113b

' S Soluble. ST= Slight tendency toward solubility. DT=Definite tendency toward solubility. VS=Very soluble.

Fhimolfiar rasimrflraaauzylilhenoti' Aliiziiyde fowrasimfil rmaidehydaa Date, June 23, 24,1948

[Rsixtmaa lmpflot plutfsize:fiatcfig-rapproximatlymmpundsyeorrespozxdingztozsmofi Imamrmwwwbutitliissbatcfi designatdmm} vent vent Lbs: 1 1 111191 1' Res I 801 Rese- Em vent E30,-

First Stllgfl -1 L Resin to EtO- Molal mam Ex. N0. 1140.

14. 2 15.8 10? 14.2 1521 33255 a.:1z-3.:4i 01 7591111 1224 50. 1501 116- N85 Fifth Staaci 1 i 1 Resin tolEtoQu} Molal Ritio 1:205 Ex; NO. 11817.]...

Starting Mix Resin .to EIZO= -1 Third 8mm 1 v V f 1 2L Resin toEt0,..

M01111 mm 1' 0- E15; No. 121D.

Fourth 51 L I B-Boluble. NS-Not soluble. vs-ve'r aolume.

Phenol for resin: Para-secondary butylphenol Aldehyde for resin: Formaldehyde Date, July 14-15, 1948 [Resin made in pilot plant size batch, approximately pounds, corresponding to 21 of Patent 2,499,370 but this batch designated 124a.]

at End of NH): VVhith is lMix 'hich Re- 1' Reaction ifie or mains as I\ext Starting Mix 8 T tarter Max. Max. Pressure Temnera- Tune Solubility lbs sq in ture 0 Lbis. gbs. Lbs abs. Tbs Ifihs. Lbs abs. Lbs So eso eso es- 0 es- A vent 1n Eto vent in Eto vent in Eto vent in Eto First Stage Resin to EtO MolalzRatio 1:10; 14.45 15.55 0 14.45 15.55 4.25 5.97 6.38 1.75 1 8.48 9.17 2.50 150 542 NS Ex. No. 124b Second Stage Resin to EtO- Moial Ratio 1:5 8 48 Ex. No. 125D Third Stage Resin to EtO Molai Ratio 1:10. Ex. No. 12611 Fourth Stage Resin to EtO.

Molal Ratio 1:15. Ex. No. 1275 Fifth Stage Resin to EtO M0121 Ratio 1 :20.

2.85 v4. 2.05 2.85 15.45 80 170 i2 VS Ex. N0. 128!) S=Soluble. N S=Not soluble. SS= Somewhat soluble. VS=Very soluble.

Phenol for resin: M enthyl Aldehyde for resin: Propionaldehyde Date, August 12-13, 1948 i [Resin made on pilot'plant size batch, approximately 25 pounds, corresponding to 81a of Patent 2,499,370 but this batch designated 129a.]

- Mix Which is Mix Which Restarting Mix gg figg of Removed [or mains as Next Sample Starter Max a I Pressure Temxgerag f Solubility 1 .1. 5. p115. Lbs I b s. abs. Lbs Lbls. I bs. Lbs ghls. Ifibs. Lbs P tum Q o teso es- So eso esvent in Eto vent in E10 'veut in Eto 1'01 in Bio First stage Resin to Eton--. Mole! Ratio 12.8 11.2 12.8 11.2 2. 75 4.25 5.7 0.95 8.55 11.50 1.80 150 15 Not. soluble. Ex.N0.129b 1 Second Stage Resin to EtO- Molal Ratio 8.55 11.50 1.80 8.55 11.50 9.3 4.78 6.42 5.2 3.77 5.08 4.10 100 170 $6 Somewhat Ex. No. b soluble. I

Third Stage Resin to EtO Molal Ratio 3 77 5.08 4.10 3.77 5. 08 13.1 100 182 M2 .Soiuble. Ex.No.131b

Fourth Stage Resin to EtO Molal Ratio 5 2 7.0 5.2 7.0 17.0 3.10 4.17 10.13 2.10 2.83 0.87 200 182 $4 Verysoluble. Ex. No. 1325-- Fifth Stage Resin to E10..-" Molal Ratio 1: 2 10 2.83 6.87 2.10 2.83 9. r 90 16 Very soluble. Ex.No.133b H Phenol Tfomresifiz: Bazaz-tertidmammylphenola- Aldehgdezforwesinrx Furfural Date, August 27-31, 1948 [Resin made onzp'iltiplumizbb'athh a'pprbximateiyz 251101111115 corresponding to 4211 of Patent2;499';370 butIthis batchrdesignated as 134a.1

Phenol for resin: M enthyl Aldehyde for resin: Furfural Date, Sept. 23-24,1948

Lbs. Sol- ;vent':

Lbs.. Eto:

First Stage? Rsinio'EtO'zl Ex. No. 139b .S'eeand-Stage:v

Resin to EtO; Molal Ratio 1 Ex.-No. 1400-..

ThirWS'taM.

Resin 16 15101.. I I M0181 Ratio 1:10.. 422 6. 98 4.22 6. 98 10.0 90 165 Soluble Ex. No. 1410 Fburth sfdag.

Resin to EtO; Molal Ratio 1 1 Ex. No. 1420.

waist-am Resin to EtOmn} 10. 25 17. 2.5 2.65 4. 66 0.65 7.6 1 13.15 1.85 150 $5 NOtSOlublG.

7.6 13.15 11.85 7.611315 9.35 5.2 9.00' 6.40 2.4 4.15 2.95 80 177 Somgwhat' solfibi.

}3. 76 6.24 3.76 6.24 13.25 171 54 Verysoluble.

Molal Ratio 1 Ex. No. 1430--.---

2.4 4.15 2.95 2.4: 4.15 11. 70' 90 Very',so1ub1e.

2,541,997 39 40 Phenol for resin: Para-octyl Aldehyde for resin: Furfural Date, October 7-8, 1948 [Resin made on pilot plant size batch. approximately 25 pounds. corresponding to 42a of Patent 2,499.370 with 206 parts by weizht of commercial para-octylphenol replacing 164 parts by weight of paratertiary amylphcnol but this batch designated as 144a.]

. Mix Which is Mix Which Re- Starting Mix 3 532 of Removed [or mains as Next Sample Starter Max. Max. Time ltljrcssure '{em geahm Solubility Lbs. Lbs Lbs. Lhs. Lbs. Lbs. Lbs. Lbs.

' Lbs. Lbs. Lbs. Lbs. Sol- Res- Sol- Res- 861- Res- 801- Resvent in Eto vent in Eto vent in Eto vent in Eto First Stage Resin to EtO M0121! Ratio 1:1 12 1 18.6 12.1 18.6 3.0 5.38 8.28 1.34 6.72 10.32 1.66 .80 150 M2 Insoluble. Ex. N0.144b-.

Second Stage Slight tend.- Resin t0 Et0 ency to; Molal Ratio 1:5-- 9 25 14. 25 9. 25 14. 25 11.0 3. 73 5. 73 4. 44 5. 52 8.52 6.56 100 177 912 ward ".1 1 Ex. No. 1450..... coming soluble.

Third Stage I Resin to Et0 M0131 Ratio 1:10. 6.72 10.32 1.66 6.72 10.32 14.91 4. 97 7.62 11.01 1. 75 2.70 3.90 85 182 A Fairly S0111- Ex. N0. 146a"-.. ble.

Fourth Stage Resin to EtO Molal Ratio 1:15. 5.52 8.52 6.56 5.52 8.52 19. S1 1 100 176 21 Readily 50]- Ex. No. 147b uble.

Fifth Stage Resin to EtO M0121] Ratio 1:20. 1 75 2. 70 3. 90 1. 75 2. 70 8. 4 80 160 111 Quite 8011b Ex. N0. 148b ble. I

Phenol for resin: Para-phenyl Aldehyde for resin: Furfural Date, October 11-13, 1948 Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 4211 of Patent 2.499 370 with 170 parts by weight of commercial paraphenylphenol replacing 164 parts by weight of para-tertiary amylphcnol but this batch designated as 14911.]

- Mix WVhich 15 Mix Which Re- Starting Mix g figg of Removed for mains as Next Sample Starter Max Pressure Temyera- Tune Solubility lbs s in ture 0 Ibls. Ifibs. Lbs I b s. gbs. Lbs Ihls. Ifibs. Lbs 1 6 s. abs. I M

o es- 0 eso eso esvent m Eto vent in E vent in E10 vent in Eto First Stage Resin to EtO MOlal Ratio 1:1 13 9 16.7 13.9 16.7 3.0 3.50 4. 0.80 10. 12. 2.20 100 160 $6 Insoluble; Ex. No. 149b Second Stage Resin to 1110..-. 2 Molal Ratio 1:5. 10 35 12.45 2.20 10.35 12.45 12.20 5.15 6. 19 6.06 5. 20 6.26 6.14 183 15 e Ex. No. 150b. fif 1 Third Stage Resin to EtO. M6161 Rat o 1=10v s 10.7 8.90 10.10 19.0 5. 30 6.38 11.32 3.60 4.32 7 0s 90 19:; 2 g Ex. No. 151b.

Fourth Stage Resin t0 EtO M01111 Riltifl 1:15. 5 20 6. 26 6.14 5.20 6.26 16.64 171 168 13 Ex.N0.152b

Fifth Stage Resin to EtO Molal Ratio 1:20. 3 60 4.32 7.68 3. 60 4.32 15. 68 Sample somewhat rnbberyand gelat- 230 170 2 Ex. N0. 153binous but fairly soluble 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING A HYDROPHILE ESTER IN WHICH THE ACYL RADICAL IS THAT OF THE FATTY ACID OF DRASTICALLYOXIDIZED CASTOR OIL, AND THE ALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILE POLYHYDRIC SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHABETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVNG NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 